CN107001674B - 功能防反射膜 - Google Patents

功能防反射膜 Download PDF

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CN107001674B
CN107001674B CN201580054666.8A CN201580054666A CN107001674B CN 107001674 B CN107001674 B CN 107001674B CN 201580054666 A CN201580054666 A CN 201580054666A CN 107001674 B CN107001674 B CN 107001674B
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silicone
film
antireflection film
graft polymer
solvent
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CN107001674A (zh
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朴世贞
赵烘宽
金章淳
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LG Chem Ltd
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Abstract

本发明提供了防反射膜，其包括：基底层；和在所述基底层的至少一个表面上形成的涂层，其中所述涂层包含组合物的固化材料，所述组合物包含可光固化(甲基)丙烯酸酯树脂、无机纳米颗粒、含有聚丙烯酸酯主链和硅氧烷侧链的硅氧烷‑丙烯酸酯接枝聚合物和溶剂。

Description

功能防反射膜
技术领域
本发明涉及功能防反射膜。
背景技术
当显示器暴露于各种照明光和自然光等时，对比度劣化(这是由于由显示器内的反射光产生的图像未能在眼睛上清楚地形成所引起的)使用户难以观看屏幕，并且导致眼睛疲劳或引起头痛。出于该原因，对防反射的需要也变得非常强烈。此外，为了提高显示器的可见度，除防反射功能以外，也已对多种功能进行了研究和开发以减少摩尔纹现象或牛顿环现象。然而，仍然难以设计用于确保防反射和多种功能而不妨碍光学特性(例如，透光率)的防反射膜。
发明内容
技术问题
本发明的一个示例性实施方案提供了防反射膜，其同时实现优异的防反射功能和牛顿环防止功能，而不妨碍其光学特性。
技术方案
本发明的一个示例性实施方案提供了防反射膜，其包括：基底层；和在所述基底层的至少一个表面上形成的涂层，其中所述涂层包含组合物的固化材料，所述组合物包含可光固化(甲基)丙烯酸酯树脂、无机纳米颗粒、含有聚丙烯酸酯主链和硅氧烷侧链的硅氧烷-丙烯酸酯接枝聚合物、和溶剂。
硅氧烷-丙烯酸酯接枝聚合物的重均分子量(Mw)可为约1000至约2500。
硅氧烷-丙烯酸酯接枝聚合物可包含量为约10重量％至约30重量％的硅氧烷侧链。
硅氧烷-丙烯酸酯接枝聚合物的硅氧烷侧链可暴露于涂层的表面。
溶剂的极性指数可为5.0或更小。
溶剂可包括选自以下的至少一者：苯溶剂、酮溶剂、醇溶剂及其组合。
可光固化(甲基)丙烯酸酯树脂的重均分子量(Mw)可为约150至约300。
无机纳米颗粒的平均粒径可为约30nm至约60nm。
无机纳米颗粒可包括选自以下的至少一者：二氧化硅颗粒、二氧化钛颗粒、氧化锆颗粒及其组合。
无机纳米颗粒可经基于硅烷的化合物表面处理。
无机纳米颗粒总表面积的约10％至约50％可经基于硅烷的化合物表面处理。
基于硅烷的化合物可包括选自以下的至少一者：3-氨基丙基三乙氧基硅烷(AOPTMS)、甲基丙烯酰氧基丙基三甲氧基硅烷(MAPTMS)、3-甲基丙烯酰氧基丙基三甲氧基硅烷及其组合。
组合物可包含量为约0.03重量％至约0.1重量％的硅氧烷-丙烯酸酯接枝聚合物。
组合物可包含量为约50重量％至约90重量％的溶剂。
固化材料可通过在约200mJ至约400mJ的光能下使组合物光固化来形成。
基底层可包括选自以下的至少一者：聚对苯二甲酸乙二醇酯(PET)、聚萘二甲酸乙二醇酯(PEN)、聚醚砜(PES)、聚碳酸酯(PC)、聚丙烯(PP)及其组合。
基底层的厚度可为约25μm至约200μm。
涂层的厚度可为约90nm至约120nm。
防反射膜还可包括在基底层的一个表面上的粘合层和离型膜层。
有益效果
防反射膜可应用于显示器等以实现牛顿环防止功能，同时确保优异的光学特性和防反射功能。
附图说明
图1示意性示出根据本发明的一个示例性实施方案的防反射膜的截面图。
具体实施方式
参照下文中将描述的实施例，本发明的益处和特征以及实现这些益处和特征的方法将变得明显。然而，本发明不限于将在下文中公开的实施例，而是可以以各种其他形式来实施，并且提供本实施例仅用于使本发明的公开内容完整，以及对本发明所属技术领域的普通技术人员完全显示本发明的范围，发明将仅由权利要求书的范围限定。在整个说明书中，类似附图标记表示类似构成元件。
本发明的一个示例性实施方案提供了防反射膜，其包括：基底层；和在所述基底层的至少一个表面上形成的涂层，其中所述涂层包含组合物的固化材料，所述组合物包含可光固化(甲基)丙烯酸酯树脂、无机纳米颗粒、含有聚丙烯酸酯主链和硅氧烷侧链的硅氧烷-丙烯酸酯接枝聚合物、和溶剂。
通常，防反射膜用于防止入射至触摸屏面板(例如，显示器)的光被反射并使可见度劣化，并且具有这样的结构：其中具有防反射功能的涂层层合在基底层上。
同时，当触摸显示器时，其中存在的两个不同基底彼此接触，结果，可能由空气层的压制导致的光的干涉而产生称作牛顿环的彩虹色环，并且牛顿环对妨碍可见度负有责任。可制造用于防止牛顿环的单独膜。然而，由于用于防止牛顿环的单独膜需要在结构上存在于与显示器内的防反射膜相同的位置，所以存在将两个膜一起使用而不能同时暴露于显示器表面的问题。
因此，根据本发明的防反射膜可通过包括单个涂层来解决所述问题并确保优异的功能，所述单个涂层同时实现防反射功能和牛顿环防止功能。
图1示意性示出根据本发明的一个示例性实施方案的防反射膜100的截面图。参照图1，防反射膜100包括基底层10；和在所述基底层10的至少一个表面上形成的涂层20。
涂层20用于同时实现防反射功能和牛顿环防止功能，并且具体地，涂层20可由组合物形成，所述组合物包含可光固化(甲基)丙烯酸酯树脂、无机纳米颗粒、具有接枝至聚丙烯酸酯主链的硅氧烷侧链的硅氧烷-丙烯酸酯接枝聚合物、和溶剂，并且更具体地，涂层20可包含所述组合物的固化材料。
硅氧烷-丙烯酸酯接枝聚合物具有接枝至聚丙烯酸酯主链的硅氧烷侧链，并且用于改善牛顿环防止功能。此外，涂层包含组合物的固化材料，但是硅氧烷-丙烯酸酯接枝聚合物用作这样的添加剂：即使在组合物固化过程期间也保持其形式而不反应。
具体地，硅氧烷-丙烯酸酯接枝聚合物的重均分子量可为约1000至约2500。硅氧烷-丙烯酸酯接枝聚合物可具有所述范围内的重均分子量，从而实现优异的牛顿环防止功能，而不与组合物的其他组分化学反应。
此外，硅氧烷-丙烯酸酯接枝聚合物可包含量为约10重量％至约30重量％，例如约20重量％至约30重量％的硅氧烷侧链。硅氧烷-丙烯酸酯接枝聚合物可包含所述范围内含量的硅氧烷侧链，并因此与溶剂相互作用，从而赋予涂层表面滑移特性并确保优异的牛顿环防止功能。当硅氧烷-丙烯酸酯接枝聚合物包含小于约10重量％的量的硅氧烷侧链时，可能难以赋予涂层表面滑移特性以便实现牛顿环防止功能。
硅氧烷-丙烯酸酯接枝聚合物的硅氧烷侧链可暴露于涂层的表面，并因此，可以赋予滑移特性以获得优异的牛顿环防止功能。具体地，可根据溶剂的极性程度来调节硅氧烷-丙烯酸酯接枝聚合物暴露于所述表面的程度。
具体地，溶剂的极性指数可为5.0或更小。“极性指数”通常表示溶剂的极性程度，并且将非极性到极性从0至10定量。溶剂的极性指数满足所述范围，使得硅氧烷-丙烯酸酯接枝聚合物暴露于涂层表面的程度得以调节，从而确保优异的滑移特性并且使牛顿环防止功能最大化。
溶剂可包括烷烃溶剂，例如戊烷、1，1，2-三氯三氟乙烷、环戊烷、庚烷、己烷、异辛烷、环己烷和二氯甲烷；醚溶剂，例如四氢呋喃和1，4-二
Figure BDA0001264636260000041
烷；苯溶剂，例如甲苯、二甲苯、氯苯和二氯苯；酮溶剂，例如甲基乙基酮、甲基丁基酮、甲基异丁基酮、二乙基酮、二丙基酮和环己酮；以及醇溶剂，例如甲醇、乙醇、异丙醇和丁醇。
具体地，溶剂可包括选自以下的至少一者：苯溶剂、酮溶剂、醇溶剂及其组合，并且在这种情况下，硅氧烷-丙烯酸酯接枝聚合物容易暴露于涂层的表面，并且可有效地改善牛顿环防止功能。
更具体地，溶剂为苯溶剂、酮溶剂和醇溶剂的混合物，所述混合物的极性指数可为5.0或更小，并且在这种情况下，可实现优异的牛顿环防止功能。
防反射膜可包含可光固化(甲基)丙烯酸酯树脂以实现优异的光学特性，并且具体地，所述可光固化(甲基)丙烯酸酯树脂可为低聚物形式。
更具体地，可光固化(甲基)丙烯酸酯树脂的重均分子量可为约150至约300。可光固化(甲基)丙烯酸酯树脂具有所述范围内的重均分子量，并因此可促进包含无机纳米颗粒的组合物的光固化，并且可实现具有适当固化度的涂层。
可光固化(甲基)丙烯酸酯树脂可包含选自以下的至少一者：多元醇；多元羧酸及其酸酐；和可通过使丙烯酸、聚硅氧烷聚丙烯酸酯、聚氨基甲酸酯(甲基)丙烯酸酯、多羟基聚(甲基)丙烯酸酯及其组合酯化而获得的聚酯(甲基)丙烯酸酯，但不限于此。
如有必要，用于形成涂层的组合物还可包含可交联单体以确保可光固化(甲基)丙烯酸酯树脂合适的交联密度，并且可包含合适含量的可交联单体。
可交联单体可包括选自以下的至少一者：乙二醇二丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、1，6-己二醇二(甲基)丙烯酸酯、三羟甲基丙烷三(甲基)丙烯酸酯、季戊四醇六(甲基)丙烯酸酯、双酚A-二缩水甘油醚的二(甲基)丙烯酸酯、氨基甲酸酯(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、三(甲基)丙烯酸甘油酯及其组合，但不限于此。
用于形成涂层的组合物用于改善分散性和透明性，并且可包含无机纳米颗粒。所述无机纳米颗粒可包括选自以下的至少一者：二氧化硅颗粒、二氧化钛颗粒、氧化锆颗粒及其组合。
无机纳米颗粒的平均粒径可为约30nm至约60nm。当无机纳米颗粒的平均粒径满足所述范围时，组合物易于涂覆至具有适于引起光干涉的厚度，并因此，可使反射率最小化，并且由所述组合物形成的涂层可确保合适的颗粒密度，从而表现出优异的机械特性。
无机纳米颗粒可经基于硅烷的化合物表面处理。无机纳米颗粒可经由所述表面处理与可光固化(甲基)丙烯酸酯树脂化学结合，并且可实现优异的分散性和耐久性。
具体地，无机纳米颗粒的颗粒表面积的约10％至约50％可经基于硅烷的化合物表面处理，并且在这种情况下，组合物可实现具有均一分散性和优异透明性的涂层。具体地，基于硅烷的化合物可包括选自以下的至少一者：3-氨基丙基三乙氧基硅烷(AOPTMS)、甲基丙烯酰氧基丙基三甲氧基硅烷(MAPTMS)、3-甲基丙烯酰氧基丙基三甲氧基硅烷及其组合。无机纳米颗粒可经基于硅烷的化合物表面处理，从而实现优异的分散性和耐久性，并且改善光学特性例如透明性。
组合物包含硅氧烷-丙烯酸酯接枝聚合物作为添加剂以用于确保牛顿环防止功能，并且具体地，可包含量为约0.03重量％至约0.1重量％的硅氧烷-丙烯酸酯接枝聚合物。硅氧烷-丙烯酸酯接枝聚合物可以以所述范围内的含量包含在内，从而确保优异的牛顿环防止功能，而不妨碍防反射功能。当硅氧烷-丙烯酸酯接枝聚合物以小于约0.03重量％的量包含在内时，难以实施牛顿环防止功能；而当硅氧烷-丙烯酸酯接枝聚合物以大于约0.1重量％的量包含在内时，可能存在这样的问题：制造涂层之后硅氧烷-丙烯酸酯接枝聚合物残留在其中，并且构成涂层的组分的结合力可能减小。
此外，组合物可包含量为约50重量％至约90重量％的溶剂。组合物包含所述范围内含量的溶剂，并因此，有利的是使硅氧烷-丙烯酸酯接枝聚合物暴露于涂层的表面，并且可有效地改善牛顿环防止功能。
此外，组合物可包含量为约1重量％至约5重量％的可光固化(甲基)丙烯酸酯树脂。此外，组合物可包含量为约5重量％至约45重量％的无机纳米颗粒。所述树脂和无机纳米颗粒以所述范围内的含量包含在内，从而实现优异的光学特性，同时改善防反射功能和牛顿环防止功能。
组合物可光固化，并且还可包含光引发剂。当组合物还包含光引发剂时，光引发剂的含量可为约0.5重量％至约1重量％。
光引发剂的类型没有特别限制，但是光引发剂可包括选自以下的至少一者，例如：α-羟基酮化合物、苯基乙醛酸化合物、苄基二甲基缩酮化合物、α-氨基酮化合物、单酰基膦(MAPO)化合物、双酰基膦(BAPO)化合物、氧化膦化合物、茂金属化合物、碘
Figure BDA0001264636260000061
盐及其组合。
涂层可包含组合物的固化材料，并且具体地，可包含组合物的光固化材料。在这种情况下，固化材料可通过在约200mJ至约400mJ的光能下使组合物光固化来形成。组合物可在所述范围内的光能下固化，由此确保合适的固化度，以表现出优异的光学特性，同时改善防反射功能和牛顿环防止功能。
参照图1，防反射膜100包括基底层10；和可在基底层10的一个表面上形成的涂层20。
基底层是透明膜，并且可包括选自以下的至少一种材料：聚对苯二甲酸乙二醇酯(PET)、聚萘二甲酸乙二醇酯(PEN)、聚醚砜(PES)、聚碳酸酯(PC)、聚丙烯(PP)及其组合。例如，基底层10可包括聚对苯二甲酸乙二醇酯(PET)，并且在这种情况下，与涂层的结合力优异，并因此，可以获得增强机械特性的效果。
基底层10的厚度可为约25μm至约200μm。基底层10具有所述范围内的厚度，因此，可用作支撑体以确保优异的耐久性而不使透明性劣化。
涂层的厚度可为约90μm至约120μm。涂层20具有所述范围内的厚度，并且可同时实现优异的防反射功能和牛顿环防止功能，而不妨碍光学特性。
防反射膜还可包括在基底层的一个表面上的粘合层和离型膜层，并且具体地，可具有离型膜层、粘合层、基底层和涂层依次层合的结构。在这种情况下，防反射膜容易地分布，并且容易地附着至在简单去除离型膜后要附着的物体，并因此，可确保方便应用于显示装置等。
当防反射膜还包括在基底层的一个表面上的粘合层时，所述粘合层可由透明粘合剂形成，并且例如，所述粘合剂可包括选自以下的至少一者：丙烯酸类粘合剂、橡胶粘合剂、硅酮粘合剂及其组合。
防反射膜在同时确保防反射功能和牛顿环防止功能的同时表现出优异的光学特性，并且具体地，反射率为约5％或更小，例如，约1.1％或更小，并且例如约1％或更小。“反射率”是通过用光照射防反射膜，被反射而不透射的光的比例的量度，并且可以看出反射率满足所述范围，并因此确保了优异的防反射功能。
此外，防反射膜的透光率可为约90％或更大，例如约95％或更大。防反射膜具有所述范围内的透光率，并因此可同时实现优异的光学特性和防反射功能。
下文中，将提出本发明的具体实施例。然而，提供下文中描述的实施例仅用于具体示例或解释本发明，并且本发明不受其限制。
<实施例和比较例>
实施例1
将10重量％的二氧化硅颗粒(其中总表面积的18％经3-氨基丙基三乙氧基硅烷(AOPTMS)表面处理)、1重量％的可光固化丙烯酸酯树脂(为聚硅氧烷聚丙烯酸酯和聚氨基甲酸酯(甲基)丙烯酸酯的混合物)、和0.94重量％的光引发剂(Ciba Co.，Ltd.，生产，Irgacure-184)混合，并且将其与88重量％的溶剂(极性指数为1.8，并且是酮溶剂、苯溶剂和醇溶剂的混合物)混合，并且向其中添加0.06重量％的硅氧烷-丙烯酸酯接枝聚合物，由此制备用于涂层的组合物。同时，制备厚度为50μm的聚对苯二甲酸乙二醇酯(PET)基底层，并将用于涂层的组合物涂覆在基底层的一个表面上，然后在300mJ的光能下固化以制备厚度为100nm的涂层，由此制备防反射膜。
实施例2
以与实施例1中相同的方式制备防反射膜，不同之处在于：使用这样的溶剂，其极性指数为7.3并且是酮溶剂、苯溶剂和醇溶剂的混合物。
比较例1
将10.055重量％的二氧化硅颗粒(其中总表面积的18％经3-氨基丙基三乙氧基硅烷(AOPTMS)表面处理)、1.005重量％的可光固化丙烯酸酯树脂(为聚硅氧烷聚丙烯酸酯和氨基甲酸酯(甲基)丙烯酸酯的混合物(或共聚物))、和0.94重量％的光引发剂(Ciba Co.，Ltd.生产，Irgacure-184)混合，并且将其与88重量％的溶剂(极性指数为1.8，并且是酮溶剂、苯溶剂和醇溶剂的混合物)混合，由此制备用于涂层的组合物。同时，制备厚度为50μm的聚对苯二甲酸乙二醇酯(PET)基底层，并将用于涂层的组合物涂覆在基底层的一个表面上，然后在300mJ的光能下固化以制备厚度为100nm的涂层，由此制备防反射膜。
[表1]
Figure BDA0001264636260000091
表1以重量％示出实施例和比较例中包含在用于涂层的组合物中的各个组分的含量。
<评估>
实验例1：反射率的测量
对于实施例和比较例中的防反射膜，制备尺寸为宽度x长度＝50mm x 50mm的样品，通过使用透射率反射率测量装置(KONICA MINOLTA，Spectrophotometer CM-5)来测量反射率，并且结果示于以下表2中。
实验例2：透光率的测量
对于实施例和比较例中的防反射膜，制备尺寸为宽度x长度＝50mm x 50mm的样品，通过使用透射率反射率测量装置(KONICA MINOLTA，Spectrophotometer CM-5)来测量透光率，并且结果示于以下表2中。
实验例3：牛顿环防止功能的测量
对于实施例和比较例中的防反射膜，制备尺寸为宽度x长度＝80mm x 120mm的样品，通过靠肉眼进行的评估来测量用于消除在将样品压在偏振膜上之后产生的牛顿环的时间，并且结果示于以下表2中。
[表2]
类别 反射率[％] 透光率[％] 牛顿环防止功能
实施例1 0.98 95.25 2秒
实施例2 1.09 95.3 15秒
比较例1 1.17 95.35 未消除
参照表2的结果，可以看出：实施例1和2中的防反射膜同时实现优异的防反射功能、光学特性和牛顿环防止功能；而比较例1不包含硅氧烷-丙烯酸酯接枝聚合物作为添加剂，并且未实现牛顿环防止功能。
[附图标记说明]
100：防反射膜
10：基底层
20：涂层

Claims (18)

1.一种防反射膜，包括：
基底层；和
在所述基底层的至少一个表面上形成的涂层，
其中所述涂层包含组合物的固化材料，所述组合物包含可光固化(甲基)丙烯酸酯树脂、无机纳米颗粒、含有聚丙烯酸酯主链和硅氧烷侧链的硅氧烷-丙烯酸酯接枝聚合物、和溶剂，其中所述组合物包含量为大于或等于0.03重量％并小于0.1重量％的所述硅氧烷-丙烯酸酯接枝聚合物。
2.根据权利要求1所述的防反射膜，其中所述硅氧烷-丙烯酸酯接枝聚合物的重均分子量为1000至2500。
3.根据权利要求1所述的防反射膜，其中所述硅氧烷-丙烯酸酯接枝聚合物包含量为10重量％至30重量％的所述硅氧烷侧链。
4.根据权利要求1所述的防反射膜，其中所述硅氧烷-丙烯酸酯接枝聚合物的所述硅氧烷侧链暴露于所述涂层的表面。
5.根据权利要求1所述的防反射膜，其中所述溶剂的极性指数为5.0或更小。
6.根据权利要求1所述的防反射膜，其中所述溶剂包括选自以下的至少一者：苯溶剂、酮溶剂、醇溶剂及其组合。
7.根据权利要求1所述的防反射膜，其中所述可光固化(甲基)丙烯酸酯树脂的重均分子量为150至300。
8.根据权利要求1所述的防反射膜，其中所述无机纳米颗粒的平均粒径为30nm至60nm。
9.根据权利要求1所述的防反射膜，其中所述无机纳米颗粒包括选自以下的至少一者：二氧化硅颗粒、二氧化钛颗粒、氧化锆颗粒及其组合。
10.根据权利要求1所述的防反射膜，其中所述无机纳米颗粒经基于硅烷的化合物表面处理。
11.根据权利要求10所述的防反射膜，其中所述无机纳米颗粒总表面积的10％至50％经所述基于硅烷的化合物表面处理。
12.根据权利要求10所述的防反射膜，其中所述基于硅烷的化合物包括选自以下的至少一者：3-氨基丙基三乙氧基硅烷、甲基丙烯酰氧基丙基三甲氧基硅烷、3-甲基丙烯酰氧基丙基三甲氧基硅烷及其组合。
13.根据权利要求1所述的防反射膜，其中所述组合物包含量为50重量％至90重量％的所述溶剂。
14.根据权利要求1所述的防反射膜，其中所述固化材料通过在200mJ至400mJ的光能下使所述组合物光固化来形成。
15.根据权利要求1所述的防反射膜，其中所述基底层包括选自以下的至少一者：聚对苯二甲酸乙二醇酯、聚萘二甲酸乙二醇酯、聚醚砜、聚碳酸酯、聚丙烯及其组合。
16.根据权利要求1所述的防反射膜，其中所述基底层的厚度为25μm至200μm。
17.根据权利要求1所述的防反射膜，其中所述涂层的厚度为90nm至120nm。
18.根据权利要求1所述的防反射膜，还包括：
在所述基底层的一个表面上的粘合层和离型膜层。
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